Continuous process for the refining of mineral oils



March 6, 1928. 1,661,826

' E. T. HESSLE CONTINUOUS PROCESS FOR THE REFINING 0F MINERAL OILS Filed Dec. 6. 1923 2 Sheets-Sheet l IN VEN TOR.

BY r

A TTORNE Y.

March 6, 1928.

Filed Dec. 6, 1923 2 Sheets-Sheav 2 IN VEN TOR.

A TTORNE Y.

Patented Mar. 6, 1928.

UNITED STATES ERIC TH. HESSLE, OF LEMONI, ILLINOIS.

CONTINUOUS PROCESS FOR THE REFINING OF MINERAL OILS.

Application filed December 6, 1923. Serial No. 678,924.

it relates to a continuous catalytic process for the conversion of these hydrocarbon oils into lower boiling products, as in the production of gasoline from petroleum.

I have found that the conversion of hydrocarbon oils into lower boiling products can be more efficiently and more economically accomplished by the use of a catalyst and at lower temperatures and pressures than by the so called cracking processes. The catalyst which I have found to be most satisfactory is tin or an alloy of tin containing a small percentage of antimony.

I have furtherfound that the catalytic decomposition of the hydrocarbon oils is most etiicient when the oils are introduced into the body of molten catalyst in the form of a fog of oil suspended in a hydrogenous g It is, therefore, an object of this invention to provide a process for the catalytic decomposition of hydrocarbon oils by passing a fog of the oils through a molten catalyst containing tin, or an alloy of tin and antimony, maintained at a temperature below the normal boiling point of the oils, whereby the conversion of the oils takes place in liquid Phase.

It is a further object of this invention to provide a process for the conversion of hydrocarbon oils, wherein the oils are subjected in the presence of hydrogen to successive decomposition and hydrogenation catalysts, whereby saturated hydrocarbons of lower boiling points are produced with a minimum loss from the formation of carbon and fixed gases.

Other and further important objects of my invention will be apparent from the disclosures in the following specification and the appended claims."

In carrying out my process I employ a form of apparatus such as is illustrated diagrammatically in the accompanying drawin s in which: 7

igure 1 is a-top plan diagrammatic view of an apparatus lay-out suitable for carrying out my process.

Figure 2 is a diagrammatic elevational view of the main reaction vessels.

The hydrocarbon oils to be treated are pumped by means of a pump 20 into a tank 1 provided with a jacket 22 by which the tank maybe heated either by means of hot water or exhaust steam. The oil passes from the tank 1 under a pressure of about eight atmospheres through a pipe A, which is heated by superheated steam passing through a jacket 21 surrounding said pipe A. As shown, the steam in the jacket 21 is first preheated in coils 23 suitably positioned in the fire box 24 of a furnace 25. Said furnace 25 is merely illustrated diagrammati' cally and may be of any suitable form or design. The furnace is preferably relatively long and narrow and formed with parallel sides of masonry 26 and 27 joined by a top wall 28. In the chamber thus formed there are set a number of reaction vessels suspended from the top wall 28 and extending sub stantially to the bottom of the chamber. The oil pumped through the pipe A passes into an atomizer 2 and thence into one of said reaction vessels 3. In the atomizer 2 the oil is directed against a counter current stream of hydrogen and superheated steam conducted to the atomizer 2 under three atmospheres pressure through a pipe 29. The atomization of the oil is so carried out that a fog of oil is thereby produced of such fine dispersion that it will remain suspended in a closed chamber for a long time. The fog of oil thus produced is conducted from the atomizer 2 through a vertical pipe 30 extending into the reaction vessel 3 and opening near the bottom thereof. Said reaction vesbaffles 32, whichmay consist of steel disks sweated on the outside of the pipe and substantially of the diameter of the reaction vessel. Said battles 32 are perforated so as to allow the oil fog issuing from the bottom of the pipe 30 to pass slowly upwardly through the'body of molten catalyst.

The temperature at which the catalyst is maintained will depend largely upon the characteristics of the oil or other hydrocarbon being treated, but in general will be between 350 and 450 0;, and preferably slightly below the normal boiling point of the oil being treated. Consequently, the decomposition of the oil is effected in liquid phase, the boiling points of the conversion products, however, being sufficiently lower than the normal boiling point of the oil to result in a vaporization of the oil fog as or before it reaches the surface of the molten catalyst.

The pressure of the fog consisting of oil, hydrogen and steam, is only slightly above atmospheric, being only suflicient to counterbalance the static head of catalyst in the reaction vessel. The vapor released from the molten catalyst fills the space above the catalyst in the head of the reaction vessel and is continuously displaced therefrom through a pipe 33 passing through the cover of said reaction vessel into a reaction vessel 4 positioned alongside of the reaction vessel 3. Said reaction vessel 4 is also partially filled with a molten catalyst of tin or an alloy of tin containing a small quantity of antimony, but no atomizeris provided for this reaction vessel. The oil vapors are conducted into the bottom of said reaction vessel 4 and pass up through the body of molten catalyst where the conversion of the oil is completed. From the reaction vessel 4 the oil vapors are conducted through a pipe 34 into a vessel 5 which is partially filled with steel turnings or shavings, said steel turnings acting as a hydrogenation catalyst to effect the hydrogenation of any unsaturated products formed in the decomposition of the iydrocarbon oils or originally present therein. From said reaction vessel 5 the oil vapors are led through a pipe 35 into av column separator 6, which may be filled with clay or china cylinders to provide a large condensing surface. The condensates from the separator 6 may be drawn off through a pipe 36 into a sampling drum 37, these Condensates being adapted for use as light lubricating oils. From the separator 6 the uncondensed vapors are led through a pipe 38 into'a vessel 7 filled with copper and nickel cuttings, these serving as catalysts for continuing the hydrogenation of the oil conversion products. A pipe 39 conducts the vapors from the tank 7 into tank Swhich is filled with material consisting of 90% fullers earth and 10% nickel, the latter being finely dispersed as by precipitation throughout the former. This material serves as a further hydrogenation medium.

The vapor from tank 8 is led through a pipe 40 into a tank 9, where it is forced through lignite coal having a very finely dispersed precipitation of metallic nickel and 2% aluminum trioxide formed thereon. From tank 9 the vapor is led through a ipe 41 into a tank 10 which serves as a ractional condenser. Products having a boiling point between 150 and 250 C. are condensed in tank 10 and drawn off through 3.

pipe 42 into a sampling drum 43. The tank 10 may be of the same construction as tank 6. The uncondensed vapors in tank 10 pass through a pipe C to a condensing coil 11 where the vapors are condensed to gasoline or similar light products and drawn off into a sampling drum 44. At the top of the coil 11 there is provided an expansion valve 53 to allow the remaining uncondensed vapors to pass through a pipe 45 into a condenser 12. Said condenser 12 is preferably maintained at about minus 10 C. and for this purpose may be surrounded by a brine solution circulated in a jacket 40. The vapor products condensed in the condenser 12 are drawn off into a drum (not shown? and the uncondensed vapors are passed tirough a pipe 48 into a tank 13. Said tank 13 may be filled with granulated coal which serves to condense substantially all of the remaining vapors. In order to recover the products condensed on the surface of the coal in tank 13, it is necessary to shut off the tank 13 as by a valve 49 and to blow steam through the coal. In order that the refining process may be continuous other tanks 50, 51 and 52 are provided which are also filled with coal and any one of which ma be connected in while one of the other tan 5, such as 13, is being blown out with steam. A dual condenser 14 is provided for condensing the products resulting from the steam blowing out process and is connected with the tanks 50, 51, 52 and 13 by line 54.

It should be noted that the reaction vessels 3, 4, 5, 7, 8 and 9 are all maintained at predetermined temperatures by means of dampers similar to the damper The preferred temperatures are substantially as follows:

Tanks 3 and 4 350 to 450 C. Tank5 300 C. Tank 7 200 C. Tanks 8 and 0 130 C.

The following example illustrates one application of my process:

If a residue of an unrefined mineral oil having a specific gravity of 0.92 and a boiling point of over 350 C. is processed in the apparatus above described, the resulting products which one may expect to obtain, are substantially as follows: gasoline, 18% kerosene, 8% lubricating oil and 4% fixed ga s. By returning the condensates from the condensers 6 and 10 to tank 1 and repeating the entire process, the amount of gasoline can be increased to over 90%.

I am aware that many changes may be made, and numerous details of the process may be varied through a wide range without departing from the principles of this invention, and I therefore do not pur ose limiting the patent granted hereon, 0t 1B1- wise than necessitated by the prior art.

against a counter current stream of hydrogen gas and steam to form a fog of oil and passing said oil fog through a deep body" of molten catalyst adapted to effect decomposition of the oil into products of lower boiling point. a

2. A process of converting hydrocarbon oils into lower boiling products; which includes the step of directing a stream of the oil against a counter current stream of hydrogen and steam under sufiicient pressure to form a true fog of oil andintroduoing said fog of oil at substantially atmospheric pressure into the bottom of a column of a molten catalyst comprising an alloy oftin and antimony maintained at a temerature of between 350 and 450 C., whereliy decomposition of the oil takes place in the liquid phase, the resulting lower boiling products being released from said catalyst in vapor form.

In testimony whereof I affix my signature.

ERIC TH. HEssLE, PH. 1); 

